Esters of -cyanoguanyliminodithiocarbonic acid



, 'sulfonic alkyl esters, and

Patented Apr. 15, 1947 PA'rsNr O C PESTERS 9 egm xzilnm m AIRBON'IC ACID Jack T. Thurston and side, Conn., assig'nors New York, N.

Company, Maine No Drawing.

I 1 4 This invention relates to new organic compounds and. to their preparation. I The new compounds of the present invention, whose preparation will be described hereinafter, may be represented formula n-s NH 11 o=r- 1 r-cN re-s in w" ch R is an alkyl' or aralkyl radical. These compounds may be of a-cyanoguanyliminodithiocarbonic acid. They are useful as insecticides; vulcanization accelerators, textile assistants,

compounds. Compounds may be prepared alkaline earth metal salt of o-cyanoguanyliminodithiocarbonate with an alkylating or aralkylating agent at temperatures notin excess of about '75 C. In doing so, we may use a wide variety havingthe structure just described 1 of diiferent types and kinds of known alkylating such as,'for example, the as and araikylatingagentsalkyl halides, aralkyl halides, alkyl sulfates, aryl the like. Representa- Application December-2o, 1943, Serial No. 514,9ss

' 12 Claims. (or. 260-551) by the. following general called alkyl and aralkyl esters and intermediates in the 15 production of resins and other useful organic by treating an alkali metal or" as acetone, followed by tive examples of these alkylating agents include'- methyl p fonate,. propyl pante, we may also employ different types and kinds of aralkylating agents such as, for exam-.

' dimethyl sulfate, methyl iodide, methyl bromide,

8 ing agent thereto, w

works on alkylation procedure. Further, as noted 85 pie, benzyl chloride, benzyl iodide, benzyl bro- -mide, p-chlorobenzyl chloride and alpha-naphthyl' methyl chloride, and other, well known aralkylating agents in the practice of this in-v vention. As a class, such aralkylating agents result in the substitution of an aralkyl group into themolecule of the compound being treated therewith in accordance with this invention. Thus, in the broad practice of this invention, we may employ either an alkylating' or aralkylating agent in preparing the new esters having the generic structural formula given ante. In general, the said agents 40 We is allowed at temperatures 0 C., and preferably,

Y., a corporation ofor alkaline earth metal salts of o-cyanoguanyliminodithiocarbonate.

The alkali metal o-cyanoguanyliminodithiocarbonates which we employ formula Ma-B\ [NH 1?:

o='N- --N-cN Q-M -s v v in which Me is es alkali metal su s" as sodium,

potassium, or lithium; or an alkaline earth metal such as barium or calcium. A very good method of preparing these compounds is described in our copending application, Serial No. 489,988, filed June 7,1948, now Patent No. 2,368,903, issued February 6, 1945.- The method consists essentially in the steps or alkaline earth metal salt of dicyandiamide in a water-miscible, non-hydroxylated solvent such,

the addition of carbon disulfide in amounts sufficient to complete thereaction. This reaction is carried out at temperatures not in excess of about 65 C; y

' In alkylating o-cyanoguanyliminodithiocarbonates to. produce the new compounds of the present invention, weordinarily prepare a solution of the o-cyanoguanyliminodithiocarbonate in water, or some other organic solvent such as thereof, and add the alkylatith stirring, while keeping the temperature below about 75 C. The reaction proceeds faster at elevated temperatures, and the reaction mixture is usually heated. Inasmuch alcohol or mixtures asthe reaction is generallyexothermic, however,

it is not always necessary to heat the reaction mixture during the entire course of the reaction. a In fact, cooling is often found necessary, after started, to prevent the temrising too high. If the temperato exceed about 75 C. for a substantial length of time, the salts of o-cyanoguanyliminodithiocarbonic acid tend to cyclize,

perature from v and different reaction products are formed. Ac-

cordingly, therefore, we carry out our alkylation if from about 10 C. to about 75 from about C. to about Because the o-cyanoguanyliminodithiocarbonates are diflicult to store for long periods of react with the alkali metal 5 time without some decomposition, we prefer to have the general of suspending an alkali metal I point to 79-80? IgIH:

and may be prepared and stored for indefinite periodswithout decomposition. It may be prepared by simply treating an alkali metal or alkaline earth metal w-cyanoguanyliminodithiocarbonate with an acid at temperatures up to 40 C. When starting with 2-thio-4,6 -diaminof 1,3,5-thiadiazine, this compound is first recon- 7 ly illustrating the procedures which maybe employed and are not intended to limit, and are not to be construed as limiting, our invention to the particular reactants and reacting conditions given. All parts are by weight unless otherwise indicated.

v EXAMPLE 1 Dimethdllz l w-cyanoguanyliminodithiocarbonate OH: I

A solution-containing 128 g. (0.542 mol) of dipotassium w-cyanoguanyliminodithiocarbonate in 250 cc. of water was prepared and 100 g. (1.11 mols) of methallyl chloride added. The mixture was stirred and heated. Soon an exothermic reaction, which required intermittent cooling, occurred. The odor of methallyl mercaptan became noticeable and a tan oil formed, After heat was no longer evolved, the mixture was refluxed 15 minutes longer and then concentrated under reduced pressure, Some oil which contained mercaptan was steam distilled. After removal of the mercaptan, the hot mixture of oil and water was poured into dilute, ice-cold sodium hydroxide conditions to produce oursolution to dissolve any remaining mercaptan. A

pasty mass formed. The water wasdecanted, fresh ice water added, and on stirring, the material solidified. After being ground with a pestle, the tan solid was filtered, washed well with water, and-dried in a vacuum desiccator. The yield of crude product was 127 g. or. 88% of theoretical. The material melted at from 60-170 ,0. Crystallization from carbon tetrachloride gave almost colorless plates melting at 73-75 C. Additional crystallization for analysis raised the melting C. The material, dimethallyl ucyanoguanyliminodithiocarbonate, was extremely soluble. in organic solvents, with the exception of li-groin, in which it was insoluble. i

. EXAMPLE 2 Dibutyl w-cyanoguanyliminodithiocarbonate CaHo-S NE E To a solutionof dipotassium w-cyanoguanyliminodithiocarbonate, prepared by dissolving a mixture of 13.2 g. (0.20 mol) of potassium hydroxide and 16.0 g. (0.10 mol) of 2-thio- 4,6- diamino-l,3,5- thiadiazine in 250,cc. of water, was added 45.6 g. (0.20 mol) of butyl-p-toluenesulfonate and cc. of Cellosolve. After being heated to 65 C. for 1% hours, the solution was concentrated under reduced pressure to a small volume and poured onto ice, which precipitated a pasty solid. The liquid was decanted, and the product washed with water and dried in an oven at 50 C. The pasty, yellow solid was dissolved in carbon tetrachloride, the solution decolorized with charcoal, filtered,.and diluted with hexane untilturbid. On standing, colorless plates of dibutyl o-cyanoguanyliminodithiocarbonate, which melted at 78-80 C., separated.

EXAMPLE 3 A solution of dipotassium w-cyanoguanyliminodithlocarbonate was prepared by dissolving 12.4 g. (0.188 mol) of 85% potassium hydroxide in 25000. of water and adding 15.0 g. (0.094 mol) of 2-thio-4,6-diamino-1,3,5-thiadiazine. After addition of 20.5 g. (0.127 mol) .ofp-chlorobenzyl chloride, the mixture was stirred and heated to 60 C. Within 45'minutes colorless solid began to separate. Heating was continued 15 minutes longer, the mixture-poured onto ice, and the solid filtered. rystallization from a mixture of 60 parts methanol and 40 parts Cellosolve gave glit tering plates of di-p-chlorobenzyl w-cyanoguanyliminodithiocarbonate, which melted at 176 C.

' EXAMPLE 4 Into a 3-necked flask equipped with a condenser, stirrer, and thermometer was placed 17.65 g. (0.10 mol) of a-naphthylmethyl chloride, 10 cc. of Cellosolve, and a solution of dipotassium w-cyanoguanyliminodithiocarbonate. The above solution was prepared by dissolving 6.6 g. (0.10 mol) of 85% potassium ,hydroxide in 100 cc. of water and adding 8.0 g. (0.05 mol) .of 2-thio-4,6- diamino-l,3,5-thiadiazine. The mixture was vigorously stirred andheated to 60 C. Within 5 minutes a gummy solid separated, and after 15 more minutes the initial yellow color of the solution had disappeared along "with all of the oily droplets of the ,alkylating agent, and the solid had become. hard and granular. The mixture was cooled and the solid filtered, washed with water, and allowed'to'dry."The yield of tan solid, melting at 178-180 v the theoretical. Crystallization from butanol gave nearly colorless dense crystals of di-a-naphthylmethyl w-cyanoguanyliminodithiocarbonate, which melted at 209-210 C. v

EXAMPLE 5 Reaction between 1,4-d2 chZTopentene- 2(HaC- CHCl-,-CH=CH-CHzCl) and dipotassium cyanoguanyliminodithiocarbonate To a solution of dipotassium w-cyanoguanyliminodithiocarbonate, prepared'by adding 16.0 g. (0.10 mol) of 2-thio-4,fi-diamino l,3,5-thiadiazine to a-solution of 13.2 g. (0.20mol) of 85% po-I,

tassium hydroxide in 150 cc. of water, was added 13.85 g. (0.10 mol) of 1,4-dichloropentene-2. The whole was stirred and maintained at a temperature of 60 C. for. 30 minutes. During this time a tan gum separated. The liquid was decanted and the gum washed several times with water'and allowed to stand. solidification did Dimethyl heated to 50 C. Heating was discontinued, and,

freshly distilled dimethyl sulfate was slowly added. The mixture was cooled to keep the temperature below 70 C. After addition was complete, the mixture was cooled, and the tan, granular solid filtered, washed well with water and placed in a. vacuum desiccator to dry and remove slight traces of mercaptan. The crude yield'oi product was 128 g. or 68% of theoretical. Purification, by dissolving the solid in isopropanol and precipitating with carbon tetrachloride, and crystallization from methanol gave colorless plates of dimethyl w-cyanoguanyliminodithiocarbonate, which decomposed at 196-197 C. Analysis gave values in close agreement with the theoretical.

EXAMPLE 7 I Dibenzyl o-cyanoguar pltminodithiocarbonate NH H c =N-- -1i-oN CtHCHrS A mixture of 480 g..('3.0 mols) of 2-thio-4,6-

CcHs-CHr-S diamino-1,3,5-thiadiazine, 400 g. (6.06 mols) of 85% potassium hydroxide, and I60 g. (6.0 mols) of benzyl chloride was heated to 60 C., after which the temperature increased spontaneously to 90 C. The mixture was then cooled and poured into ice water, whereupon the reaction product solidified. The crude dibenzyl w-cyanoguanyliminodithiocarbonate was then dissolved in hot isopropanol, and the solution treated with activated charcoal and filtered. On standing,

colorless crystals of dibenzyl w-cyanogua-nyliminodithiocarbonate separated from the solution. 75

' when recrystallized from methanol, with addi- C. was 21.5 g. of 97.5% of tion of carbon tetrachloride and naphtha, colorless needle-like crystals, having a melting point of 119-120 C., were obtained. Chemicalanak ysis of the product indicated that it was practically pure dibenzyl w-cyanoguanyliminothiocab,

bonate. I

' EXAMPLE 8 Dibenzyl w-cuanoguanyliminodithiocarbonate A mixture, consisting of 160 g. (1mol 01-2- thio-4,6-diamino 1,3,5-thiadiazine, 350 g. (1.1 mols) of barium hydroxide octahydrate, and 253 g. (2.0 mols) of benzyl chloride, was heated'to' 35C. andthen-cooled and allowed to react tor several hours. During this time the reaction mixture was'maintained at a temperziturenotv in excess oi. 40 C. by cooling it occasionally. The

oil-like material initially present solidified to a light yellow, granular solid. This product was dissolved in hot isopropanol, treated with acti vated charcoal, filtered, and cooled, whereupon crystals of dibenzyl w-cyanoguanyliminodith'iocarbonate "separated from solution. The product i was dissolved in methanol andff' se-crystallized as 'before. The final product wasffound-to'bedibenzyl w-cyanoguanyliminodithiocarbonate oi! good purity.

EXAMPLE 9 Dibenzpl w-czmnoguanyliminodithiocarboriate 1 v A mixture of 160 g. (1 mol) of 2-thio.-4,6-di-- amino-1,3,5-thiadiazine, 81.5 g. (1.1'mols) of calciumhydroxide, and 253 g. (2.0 mols) ofbenzyl' chloride was stirred and heated at 35-37"C. for 6 hours. The pasty, tan-colored solidwas filtered and driedina vacuum desiccator. tion of the product'was then purified by recrystallization in the manner described in the,

previous examples. Dibenzyl w-cyanoguanyliminodithiocarbonate of an excellent degree of purity was obtained with a final over-all yield of Examu'. 10

Dibenzyl w-cyanoguanyZiminodithiocarbonate "A mixture of 160 g. (1.0 mol) oi2-thio-4,6-

- diamino-1,3,5-thiadiazine, 152 g. (1.1 mols) potassium carbonate, and 253 g. (2.0 mols) o1 benzyl chloride was heated at 50 C. for 2 hours, after which the temperature was raised to-65 C.

for one-half hour. After being cooled, the mixture was poured into ice water, whereupon the oil-like reaction product solidified to a brown,

slightly sticky solid, having a mercaptan odor.

The product was re-crystallized several times from hot alcohol to obtain pure crystals of (11'? benzyl w-cyanoguanyliminodithiocarbonate in an over-all yield of better than 50% of theoretical.

'We claim:

1. Compoundshaving the general formula R-S-\ r m r c=N+t:-N-cN v in which Ris a member of the group consisting of alkyl and aralkyl radicals.

2. Compounds having the general formula B.--S NH H 0=N -l X-CN a-s in which R is an alkyl radical.

3. Dimethyl w-cyanoguanyliminodlthiocarbonate.

A por- 4. Compounds having the general formula R-CHr-S NE E R-CHr-S in which R is an aryl radical.

s. Dibenzyl u-cyanoguanylim inodithiocarbonate. v

6.'A method 'otprepa'ring dibenzyl w-cyano guanyliminocarbonate which comprises the step of mixingtogether a benzyl halide with a compound of the group consisting oi alkali metal 40- v cyanoguanyliminodithiocarbonates and alkaline earth metal w-cyanoguanyliminodithiocarbonate and allowing the mixture to react at a temperature not in excess of about 75 C.

(VA method of preparing dibenzyl m-cyanoguanyliminodithiocarbonate which comprises the halides, alkyl sulfates and aryl sulfonic alkyl esters with a compound of the group consisting of alkali metal and alkaline earth metal'salts or w-cyanoguanyliminoditl'iiocarbonic acid.

.9.rA method of preparing compounds of the group'consisting of diallwl and diaralkyl esters oi, w-cyanoguanyliminodithiocarbonic acid which comprises the step of mixing together a member or the group consisting of alkyl halides, aralkyl halides, alkyl sulfates and aryl sulionic valkyl es-- a terswith dipotassium o-cyanoguanyliminodithio-.

carbonate.

10. A method of preparing compounds of the group consisting or dialkyl and diaralkyl esters ot D w-cyanoguanyliminodithiocarbonic acid which comprises the steps ofmixing together a member of the group consisting of alkyl halides, aralkyl halides, alkyl sulfates and aryl sulionic alkyl esters with disodium oc-cyanoguanyliminodithiocarl0 bonate.

11. A method of preparingdiaralkyl esters of w-cyanoguanyliminodithiocarbonic acid which comprises the step or mixing together an aralkyl halide with an alkali metal w-cyanoguanylimino- 15 dithiocarbonate and allowing the mixture to react at a temperature not in excess of about 75 C.

' 12. A method of preparing dialkyl esters of ucyanoguanyliminodithiocarbonic acid which comprises the step of mixing together an alkyl halide g0 and an alkali metal u-cyanoguanyliminodithiocarbonate and allowing the mixture to react at a temperature. not in excess 01' about 75 C. g i v JACK T. THURSTON.

DONALD w. KAISER.

REFERENCES crr'En The following references are of record the .file of this patent:

30 UNITED BTA'IEQPATENTS Number i Name Date 1,726,648 Cadwell -Sept. 3, 1929 :Organic Chem. Richter (Spielman), vol. 1, endEd. D. 205. I K 1 Cadwell Nov. 19, 1929 35 OTHER REFERENCES 

